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Abstract:

A fuel composition and the process of making the fuel composition are
described. More specifically, a novel biomass derived low sulfur bunker
fuels composition and the method of making thereof. Embodiment of the
invention discloses a novel low sulfur bunker fuels composition derived
from blending various bio-oil with other heavy residual fuel oils and
distillates where final sulfur content and carbon intensity is controlled
by the ratio of bio-oil to other heavy residual fuel oils and
distillates. Embodiment of the invention also discloses a process of
making a novel biomass derived low sulfur bunker fuels by blending
various bio-oil with other heavy residual fuel oils and distillates.

Claims:

1. A blended fuel composition comprising a renewable based fuel and a
petroleum based fuel, wherein the weight ratio of said renewable based
fuel to said petroleum based fuel is from 1:20 to 20:1.

2. The blended fuel composition of claim 1, comprising less than 1.5 wt %
of sulfur wherein the viscosity of said composition is less than 150 cSt
the flash point of said composition is at least 80.degree. C., and the
ash content of said composition is less than 350 ppm.

3. The blended fuel composition of claim 1, wherein said renewable based
fuel comprises a bio-oil component and a bio-co-solvent component.

11. The blended fuel composition of claim 1, further comprising a step of
pre-treatment wherein said renewable based fuel is pre-treated by
filtration, neutralization and distillation prior to admixing with said
petroleum based fuel to remove a stream comprising metals, water or
sediment, and to neutralize any acidic components.

12. The blended fuel composition of claim 1, wherein said renewable based
fuel is about 0.5 to 50% by weight of said blended fuel.

13. The blended fuel composition of claim 1, wherein the weight ratio of
said bio-oil component to bio-co-solvent component is from 2:1 to 25:1.

14. A process for producing a blended fuel composition comprising: a)
providing a renewable based fuel, b) providing a petroleum based fuel,
and c) admixing said renewable based fuel and said petroleum based fuel
in weight ratio ranges from 1:20 to 20:1.

15. The blended fuel composition of claim 14, comprising less than 1.5 wt
% of sulfur wherein the viscosity of said composition is less than 150
cSt the flash point of said composition is at least 80.degree. C., and
the ash content of said composition is less than 350 ppm.

16. The blended fuel composition of claim 14, wherein said renewable
based fuel comprises a bio-oil component and a bio-co-solvent component.

24. The blended fuel composition of claim 14, further comprising a step
of pre-treatment wherein said renewable based fuel is pre-treated by
filtration, neutralization and distillation prior to admixing with said
petroleum based fuel to remove a stream comprising metals, water or
sediment, and to neutralize any acidic components.

25. The blended fuel composition of claim 14, wherein said renewable
based fuel is about 0.5 to 50% by weight of said blended fuel.

26. The blended fuel composition of claim 14, wherein the weight ratio of
said bio-oil component to bio-co-solvent component is from 2:1 to 25:1.

27. A blended fuel composition produced by: a) providing a renewable
based fuel, b) providing a petroleum based fuel, and c) admixing said
renewable based fuel and said petroleum based fuel in weight ratio ranges
from 1:20 to 20:1.

28. The blended fuel composition of claim 27, comprising less than 1.5 wt
% of sulfur wherein the viscosity of said composition is less than 150
cSt the flash point of said composition is at least 80.degree. C., and
the ash content of said composition is less than 350 ppm.

29. The blended fuel composition of claim 27, wherein said renewable
based fuel comprises a bio-oil component and a bio-co-solvent component.

37. The blended fuel composition of claim 27, further comprising a step
of pre-treatment wherein said renewable based fuel is pre-treated by
filtration, neutralization and distillation prior to admixing with said
petroleum based fuel to remove a stream comprising metals, water or
sediment, and to neutralize any acidic components.

38. The blended fuel composition of claim 27, wherein said renewable
based fuel is about 0.5 to 50% by weight of said blended fuel.

39. The blended fuel composition of claim 27, wherein the weight ratio of
said bio-oil component to bio-co-solvent component is from 2:1 to 25:1.

Description:

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a non-provisional application which claims the
benefit of and priority to U.S. Provisional Application Ser. No.
61/506,239 filed Jul. 11, 2011, entitled "Advanced, Cellulosic,
Low-Sulfur Bunker Fuels," which is hereby incorporated by reference in
its entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

[0002] None.

FIELD OF THE DISCLOSURE

[0003] This present invention relates generally to a fuel composition.
More specifically, the present invention relates to a novel biomass
derived low sulfur bunker fuels composition and the method of making
thereof.

BACKGROUND OF THE DISCLOSURE

[0004] Bunker fuel in general refers to class of marine transportation
fuels. Traditionally, these fuels were highly viscous fluids primarily
composed of heavy petroleum fractions designed to burn in large,
low-speed diesel engines for large shipping vessels. The bunker fuel was
made up of heavy residual fuel oil (RFO) or "HFO". In the past when
refining complexity was much lower (e.g. "topping facilities"), bunker
fuel was sometimes referred to as "fuel oil No. 6", "residual", "boiler
fuel" or "Bunker C" Bunker fuels were used for both steam (boiler)
powered vessels and for diesel power vessels. Because of plant efficiency
(40-45%) steam plants over time were replaced by more efficient diesel
engines (50%). Modern low-speed, direct drive, diesels are more efficient
than medium speed engines, which require some sort of gear box or
electric drive. Modern medium speed diesels are capable of burning
heavier, more viscous "bunker" fuels.

[0005] Bunker fuel is mainly used directly in compression ignition, as
well as, boiler combustion applications for on-board power generation in
the marine and shipping industry. This traditionally heavy type of bunker
fuel is used in 80% of the world's merchant fleet that utilize ocean
routes. It is also used widely for stationary power and utility
applications by developing nations. Historically, bunker fuel was used
for boiler combustion, which produced steam. This was used in turn in
turbines to power the ships propeller and in generators to produce ship's
electricity. The steam was also used to heat the ship's fuel. In a diesel
powered ship steam either comes from waste heat boilers (economizers)
that capture the residual heat left in diesel exhaust or from auxiliary
boilers fired on heavy fuel or diesel.

[0006] Modern bunker fuel can be separated into two types: marine residual
fuels and marine distillates as outlined under the 2005 3rd edition
of ISO 8217 standard for Class F marine fuel specification. Marine
residual fuel is often referred to as intermediate fuel oil (IFO) which
is generally a combination of heavy fuel oil (HFO) diluted with other
lighter oil and/or distillate stocks to meet viscosity specifications.

[0008] The other 20% of the bunker fuels used primarily aboard smaller
vessels are marine distillates often designated as marine diesel oils
(MDO) or marine gas oils (MGO). Most are simply combinations of middle
distillate fuel oils mentioned above such as, AGO No. 1, No. 2, diesel
No. 2 (ULSD), heating oil No. 2, LCO, LCGO and hydrocracker diesel (HCD)
to be used in small engines for generating auxiliary power. Smaller
watercraft such as ferries, fishing boats and some military ships use
marine diesel only. These fuels are very closely related, if not the same
in most cases, as non-road, locomotive, marine (NRLM) finished diesel
products. The use of MDO on large vessels is fairly undefined. Most large
ships have MDO in their fuel tanks for emergency diesel generators. This
is because the MDO fuel does not require special heating. If some vessels
operate in cold climates, special MDO fuels are blended for these extreme
conditions. In the case of special equipment, such as Inert Gas
Generators, MDO may be the fuel of choice, because it is more easily
handled and burns cleaner with less effort. Finally, another application
for MDO use is within ship incinerators.

[0009] Current Bunker fuel emission levels are projected to have
significant contribution (>20%) by 2020 to the overall transportation
fuel-derived emissions inventory as other industry sectors (e.g. on-road,
off-road, stationary) become more compliant around the world. Further,
the maritime industry was not originally included in the Kyoto protocol.
Therefore, the targeted emitted species are oxides of sulfur (SOx) and
greenhouse gases (i.e., CO2, CH4, and N2O) at the moment.
Oxides of Nitrogen (NOx) and particulate matter (PM) are expected to take
priority at a later date (>2012).

[0010] However, more attention has been given to SOx since a strong
precedence has already been established with both on-road and stationary
source restrictions around the globe for many years now. SOx is
considered the "low-hanging fruit" of emissions policy. In 2008, global
SOx emissions for registered fleets was estimated at 9 teragrams (Tg). As
a result, a global cap was placed on the total amount of sulfur allowed
in bunker fuel. The International Maritime Organization (IMO) recently
established a North American Emission Control Area (ECA). As of Aug. 1,
2011, bunker fuel burned within 200 nautical miles of all coastlines in
the U.S. and Canada must contain no more than 10,000 ppmw of sulfur. By
2015, this limit will reduce to 1000 ppmw. Outside of the ECA regions,
the global cap on bunker sulfur content must remain below 35,000 ppmw by
Jan. 1, 2012 and below 5000 ppmw by 2020. Currently, a commercial, market
grade of low-sulfur bunker must contain less than 15,000 ppmw sulfur.

[0011] Greenhouse gas (GHG) restrictions will be much more difficult to
administer and implement, however, this fact will not stop future
legislation and rulings over the next few years in the U.S. and in
Europe. The IMO has developed a guideline for using a greenhouse gas
emission index for ships. In the U.S., residual based transportation fuel
accounts for over 1% of the GHG emissions which were roughly 1,633
million metric ton for 2007. Current reports have the global shipping
industry responsible for 3-5% of the global GHG emissions and nearly
15-20% by 2050.

[0012] It is highly likely that most governments around the world will
impose a tax on GHG emissions from burning bunker fuel aboard ships. At
some point in the future, shipping will contribute significantly to the
inventory of GHG, NOx, SOx, and PM.

[0013] There is also a national interest in the discovery of alternative
sources of fuels other than from petroleum resources. As the public
discussion concerning the availability of petroleum resources and the
need for alternative sources continues, government mandates will require
fuel range hydrocarbons to include, at least in part, hydrocarbons
derived from sources besides petroleum.

[0014] It would therefore be a significant contribution to the art and to
the economy to develop a low sulfur bunker fuel composition using
renewable sources such as biomass in order to meet the government fuel
regulation on pollutant emissions and to reduce a potential tax
obligation on GHG emissions (also known as carbon tax).

BRIEF SUMMARY OF THE DISCLOSURE

[0015] This present invention relates generally to a fuel composition and
the process of making thereof. More specifically, the present invention
relates to a novel biomass derived low sulfur bunker fuels composition
and the method of making thereof.

[0016] Embodiment of the invention discloses a novel low sulfur bunker
fuels composition derived from blending various biomass derived oils (or
bio-oil)/by-products with other heavy residual fuel oils and distillates
where final sulfur content is controlled by the ratio of bio-oil to other
heavy residual fuel oils and distillates.

[0017] Embodiment of the invention also discloses a process of making a
novel biomass derived low sulfur bunker fuels by blending various-biomass
derived oils/by-products with other heavy residual fuel oils and
distillates.

[0018] In one embodiment of the present invention, there is provided a
blended fuel composition comprising a renewable based fuel and a
petroleum based fuel. The weight ratio of the renewable based fuel to the
petroleum based fuel is from 1:20 to 20:1.

[0019] In another embodiment of the present invention, a method is
provided for preparing a blended fuel composition comprising blending a
renewable based fuel with a petroleum based fuel in a ratio ranges from
1:20 to 20:1.

[0020] In yet another embodiment of the present invention, a blended fuel
composition is provided from blending a renewable based fuel with a
petroleum based fuel in a ratio ranges from 1:20 to 20:1.

[0021] The major advantage of this invention is to use a relatively
inexpensive biomass to generate compounds that could be blended in
current marine bunker fuels and contribute to the overall reduction of
GHG emissions during ship transportation from a Life Cycle Assessment
(LCA) view point. It is discovered in this invention that both the tax
obligation and pollutant emissions can be reduced if the viscosity
cutters and distillates are derived from a biomass source.

[0022] Therefore, the cost advantage in both price and carbon tax
avoidance is unique to this novel bio-based low sulfur bunker fuel
composition.

[0023] Other objects, advantages and embodiments of the invention will be
apparent from the following detailed description of the invention and the
appended claims.

[0025] Turning now to the detailed description of the embodiments of the
present invention. It should be understood that the inventive features
and concepts may be manifested in other arrangements and that the scope
of the invention is not limited to the embodiments described or
illustrated. The scope of the invention is intended only to be limited by
the scope of the claims that follow.

[0026] In one embodiment, a renewable based fuel may comprise hydrocarbons
that are derived from natural, replenishable feed stock which can be
utilized as source of energy. These renewable hydrocarbons are simple in
structure and may contain molecular oxygen as represented in the general
formula of CxHyO.sub.z where 1<x<20, 2<Y<44, and
1<z<3 including the following organic classes; alcohols, ketones,
aldehydes and acids.

[0027] According to one embodiment, a renewable based fuel comprises a
bio-oil component and a bio-co-solvent component. Any oxygenated bio-oil
feedstock may be used in the present invention. The bio-oil component may
include but is not limited to pyrolysis oil produced by a pyrolysis
process.

[0028] Pyrolysis is the chemical decomposition of biomass by heating in
the absence of oxygen. U.S. Pat. No. 4,891,459, the contents of which are
herein incorporated by reference in their entirety, describes one basic
exemplary approach for the pyrolysis of biomass. Pyrolysis may be
conducted at a variety of temperatures and pressures, with or without
inert gases. Many different pyrolysis conditions are known in the art.

[0030] The composition of bio-oil is dependent upon the biomass used for
pyrolysis and conditions, but bio-oil will typically include derivatives
of lignins, cellulose, hemi-cellulose, fiber, starches, sugars, proteins
and other components not readily soluble during typical biomass
processing, milling, pulping, gasification and the like.

[0031] Bio-oils produced from biomasses are a chemically complex mixture
of compounds comprising generally a mixture of water, light volatiles,
and non-volatiles. As a fuel, bio-oil has a number of negative properties
from a transportation fuel perspective such as thermal unstability, high
acidity (corrosiveness), substantial water content (usually in the range
of 15% to 30%), poor miscibility with hydrocarbon fuels, variable
viscosity, low heating values (about half that of a typical diesel fuel),
high oxygen content and low cetane number. These negative properties are
related to the oxygenated compounds contained in bio-oils that result in
a 45 wt % oxygen content. In one embodiment, raw bio-oils may be
pretreated before they are blended or used as a renewable fuel.
Pretreatment may include filtration, neutralization and distillation
prior to admixing with said petroleum based fuel to remove a stream
comprising metals, water or sediment, and to neutralize any acidic
components.

[0032] In one embodiment, the pyrolysis bio-oil initially containing 30 wt
% water was first partially dehydrated down to 6.4 wt % water on a rotary
evaporator, then filtered overnight using Whatman #1 (11 micrometer
pores) cellulosic filter paper. The filtrate was noticeably clearer
afterwards. This filtered bio-oil was mixed with cyclohexane in a 1:1
volume ratio and charged to a pot flask. This mixture underwent
lab-scale, batch azeotropic, vacuum distillation until almost all of the
cyclohexane and moisture were removed. The weight of dehydrated bio-oil
was recorded. The final water content was roughly 0.14 wt %.

[0033] According to one embodiment of the invention, the pretreated
bio-oil is blended with a polar, bio-derived co-solvent (bio-co-solvent)
before sending to a heated storage tank. The addition of co-solvents to
the final fuel blend is optional, and the type and concentration may be
dependent on the blending methodology.

[0038] According to one embodiment petroleum residual fuel oil (RFO) may
be obtained from refining and optionally hydroprocessing a crude
petroleum source. It may be a single stream obtained from such a refinery
process or a blend of several heavier petroleum fractions obtained by
refinery processing via different processing routes.

[0039] The blended fuel composition to which the present invention is to
use includes but is not limited to a marine low-speed diesel engine, for
example a 380 cSt intermediate fuel oil (IFO) composition which is used
in large cylinder bore (>500 mm) marine diesel engines manufactured by
companies such as MAN, Wartsila and Rolls Royce. These engines are power
plants capable of moving bulk carriers, large tankers and container
vessels by delivering more than 50 kW. Therefore, the petroleum based
component may be any known residual fuel oil (RFO), and it may itself
comprise a mixture of various heavy petroleum components. It may also
have a sulfur content of at least 3.5 wt %.

[0040] During the research and development efforts to evaluate various
fuel properties of the petroleum fuels, renewable fuels, and their
blends, it was discovered that a combination of renewable based fuel and
petroleum based fuel resulted in a low sulfur fuel, provided the weight
ratio of renewable based fuel to petroleum based fuel ranges from 1:20 to
20:1.

[0041] The invention can be practiced at a high renewable based fuel
concentration, wherein the renewable based component is up to 100% by
weight of the finished fuel blend. However, in the scope of the
invention, the renewable based component is typically up to about 15% by
weight of the finished fuel blend, more typically up to about 25% by
weight of the finished fuel blend, and alternatively up to about 50% by
weight of the finished fuel blend. The invention is also applicable at
renewable based component concentrations as low as about 1, 5, and 10% by
weight of the finished fuel blend, and even at very low renewable fuel
concentrations as low as about 4, 3, 2, 1, and 0.5% by weight of the
finished fuel blend. A typical weight ratio of renewable fuel to
bio-co-solvent is 2:1 and may be as high as 25:1.

[0042] Several compositions for both heavy fuel oil (HFO) and marine
diesel oil (MDO) bunker fuel are given by blending various biomass
derived oils/by-products with residual fuel oil and distillates.

[0043] The cost advantage in both price and carbon tax avoidance is unique
to this novel bio-based low sulfur bunker fuel composition. It is
discovered in this invention that both the tax obligation and pollutant
emissions can be reduced if the viscosity cutters and distillates are
derived from a biomass source.

[0044] The major advantage of this invention is to use a relatively
inexpensive biomass to generate compounds that could be blended in
current marine bunker fuels and contribute to the overall reduction of
GHG emissions during ship transportation from a Life Cycle Assessment
(LCA) view point.

[0045] Lifecycle GHG emissions of marine bunker fuels refer to emissions
associated with the extraction and transport of crude oils, the
production of bunker fuels at the refineries, the transport of bunkers
fuels to the marine vessels, and the direct combustion of the bunker
fuels to provide power on the marine vessels. Current U.S. regulations do
not account for GHG emissions associated with the manufacturing of the
marine vessels or the engines that use bunker fuels as feeds, nor do they
account for the GHG emissions associated with the building of
infrastructure.

[0046] Similarly, lifecycle GHG emissions for the biomass-derived fuels
refer to emissions associated with the production, harvest, collection,
storage, and transport of biomass to biorefineries, the conversion of
biomass to a liquid transportation fuel at the biorefineries, the
transport of the biomass-derived fuels to the blending terminals, the
blending of the biomass-derived fuels and the marine bunker fuels into
finished products, the delivery of the fuel products to the marine
vessels, and the combustion of the fuels.

[0048] In addition, the present invention discloses that this novel fuel
composition would lead to significant reduction of sulfur and/or PM
(i.e., less than 1.5 wt % sulfur and 25% less ash content compared to
current fuel specifications) in compliance with IMO regulation, providing
a premium price advantage to the final fuel products.

[0049] The following examples are presented to further illustrate the
present invention and are not to be construed as unduly limiting the
scope of this invention.

[0050] The examples used in this disclosure centers around bio-oil
produced from the pyrolysis of woody or herbaceous biomass.

Example

[0051] Bio-oil generated from wood or other biomass sources such as, grain
fibers or hulls is sent to a pre-treatment unit to remove any metals,
water, and sediment and to neutralize any acidic components. This
pre-treated bio-oil is blended with a polar, bio-derived co-solvent and
sent to a heated storage tank. High-sulfur (>3 wt %) residual fuel oil
(RFO) is sent from a near-by refinery into another heated storage vessel.
The two oils are blended to produce a low-sulfur (<1.5 wt %) advanced
cellulosic bunker fuel (LSFO)

[0052] As shown in Figure Table 1, high sulfur (1.85%), commercial RMG 380
bunker fuel is used to create Blend A. The composition is a 3:1 ratio of
RMG to treated bio-oil/co-solvent mixture. Neither the untreated bio-oil
nor the bio-co-solvent contains sulfur. After pre-treatment with the
addition of a co-solvent, Blend A qualifies as reduced carbon, low-sulfur
(<1.5 wt %) blend with a minimum greenhouse gas (GHG) reduction of 6%
as determined by life cycle assessment. Blend A has a lower viscosity
(148 cSt), higher flashpoint (78 C) and reduced ash content (330 ppm).

[0056] In closing, it should be noted that the discussion of any reference
is not an admission that it is prior art to the present invention,
especially any reference that may have a publication date after the
priority date of this application. At the same time, each and every claim
below is hereby incorporated into this detailed description or
specification as an additional embodiment of the present invention.

[0057] Although the systems and processes described herein have been
described in detail, it should be understood that various changes,
substitutions, and alterations can be made without departing from the
spirit and scope of the invention as defined by the following claims.
Those skilled in the art may be able to study the preferred embodiments
and identify other ways to practice the invention that are not exactly as
described herein. It is the intent of the inventors that variations and
equivalents of the invention are within the scope of the claims whiles
the description, abstract and drawings are not to be used to limit the
scope of the invention. The invention is specifically intended to be as
broad as the claims below and their equivalents.